Biocidal N-chloro-amidines

ABSTRACT

New N-chloro-amidines, their manufacture and utility in combating i.a. phytopathogenic fungi. The compounds correspond to the formula   WHEREIN R represents hydrogen, alkyl or cycloalkyl, X represents -C N, -CC13 or -CC12-C N, Y represents -CC12- and n represents 0 or 1.

United States Patent [191 Petitpierre et a1.

[11 1 3,868,419 Feb.'25, 1975 1 1 BIOCIDAL N-CHLORO-AMIDINES I73] Assignce: Ciba-Geigy Corporation, Ardsley,

22 Filed: Apr. 25, 1974 211 App]. No.: 464,271

Related U.S. Application Data [62] Division of Ser. No. 279,409, Aug. 10, 1972, Pat. No.

[30] Foreign Application Priority Data Sept. 3, 1971 Switzerland 1 2945/71 July 11, 1972 Switzerland 10361/72 [52] U.S. Cl. 260/564 R, 424/326 [51] Int. Cl. C07c 123/00 [58] Field of Search 260/564 R [56] References Cited UNITED STATES PATENTS 2,364,074 12/1944 Hunt 260/564 R 3,673,252 7/1972 Coor 260/564 R OTHER PU BLlCATIONS Chemical Abstr., V01. 44, Column 9346(i), 9347(a), (1950).

Primary Examiner-Bernard Helfin Assistant Examiner-Gerald A. Schwartz Attorney, Agent, or FirmHarry Falber [57] v ABSTRACT New N-chl oro-amidinegtheir manufacture and utility in combating i.a. phytopathogenic fungi. The compounds c.orrespond to the formula wherein R represents hydrogen, alkyl or cycloalkyl, X represents -C=N, -CC.1 or -CCl -C=N, Y represents -CC1 and n represents 0 or 1.

7 Claims, No Drawings control.

The N-chloro-amidines correspond to the formula NH-R I X C N C1 wherein R represents hydrogen, alkyl or cycloalkyl, X represents C a N, CCI or -CCl -C 5 N, Y represents CCl and n represents or I.

The alkyl groups represented by R possess l to 6, in particular I to 4, carbon atoms and may be branched or straight-chain. Examples of such groups include: methyl, ethyl, propyl, isopropyl, n-, i-, sec. and tert.butyl. The cycloalkyl groups represented by R possess 3 to 8, preferably 3 to 6, ring carbon atoms. Examples of such groups include: cyclopropyl, cyclohexyl.

Preferred compounds on account of their activity are those of the formula I or II, wherein R represents hydrogen, C -C alkyl, cyclopropyl or cyclohexyl, X represents --C H N, -CCl or CCl C N, Y represents CCl and n represents 0 or I.

The N-chloro-amidines are manufactured by reacting the compounds of the formulae c1 c1 at I X-C=N-C1 or C1-N=C[Y]C=N-C1 (III) (1v) with an amine of the formula H N-R (V) wherein R, X, Y and n have the meanings given for formulae I and II, in the presence of an acid binding agent.

Suitable acid binding agents are tertiary amines, e.g. trialkylamines, pyridine, dialkyl anilines, inorganic bases, such as hydroxides; carbonates and bicarbonates of alkali and alkaline earth metal. The process is carried out at a temperature between 0 and 30C, at normal pressure and in solvents or diluents.

Examples of suitable solvents or diluents are: ethers and ethereal compounds, such as diethyl ether, dioxan, di-methoxy ethane, tetrahydrofuran; amides such as N,N-dialkylated carboxylic amides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform, chlorobenzene; nitriles, such as acetonitriles; dimethyl sulphoxide, ketones, such as acetone, methyl ethyl ketone.

It is also possible to use water or a mixture of the above cited solvents for the reaction.

The starting materials of the formulae III and IV are known or may be manufactured by analogous methods.

The compounds of the formulae I or II have a broad biocidal activity and may be used for combating plant and animal pests of various kinds.

Preeminent, however, is the combating of representatives of the division Thallophyta, e.g. bacteria and fungi, in particular of plant pathogenic fungi in cereals,

maize, rice, vegetables, vines, ornamental plants, fruit and other cultures. The compounds of the formula I are thus active against the following series of fungi:

Omycetes, Zygomycetes; Endomycetales; Aspergillales; Microascales; Protomycetales; Erysiphales, Taphrinales; Pezizales; I-Ielotiales, Phacidiales; Sphaerialles: Clavicipitales: Myriangiales; Dothiorales; Pseudospariales; Aphyllophorales: Tremellales; Auriculariales; Uredinales and Ustilaginales.

The compounds of the formulae I and I] display likewise good activity against fungi which attack the plants from the soil and partially cause trachemoycoses.

According to the invention, it is possible to treat and effectively protect against attack by fungus all kinds of seed, e.g. wheat, rye, barley, oats, maize, rice, cotton, sugar beet, vegetables; alsoseed potatoes, sugar cane cuttings, ground nuts or flower bulbs, whereby the combating of practically all phytopathogenic fungi and their spores, which damage, seed present in the soil and lead'to sever parasitic plant diseases, is made possible.

The fungicidal action of the compounds of the formulae I and II can be substantially broadened by the addition of other fungicides and adapted to the given circumstances. The following compounds are examples of suitable additives: elementary sulphur ammonium polysulphide and metal polysulphides boric acid and borates nickel sulphate potassium chromate copper (I) oxide (KUPFEROXID) Bordeaux broth and further inorganic and organic copper salts bis-(tri-n-butyl tin)oxide triphenyl tin hydroxide (FENTINHYDROXID) triphenyl tin acetate (FENTINACETAT) and further organic tin compounds methyl mercury-8-hydroxyquinolate (Ortho LM) N-(methyl mercury)-l,4,5,6,7,7-

hexachlorobicyclo[2.2. l ]hept-5-ene-2,3- dicarboximide N-(ethyl mercury)-l,4,5,6,7,7-

hexachlorobicyclo[2,2. l ]hept-5-ene-2,3- dicarboximide N-(ethyl mercury)-p-toluenesulphonic anilide phenyl mercury acetate (PMA phenyl mercury urea mixture of ethyl mercury-2,3-dihydroxypropyl mercap- 3 -ethyl-S-benzyl-phenyl-phosphonate diethylamido-benzenethiophosphonic-2-methylimidazolide methylbromide methyl isocyanate 1,3-dichloropropene and related halogenated C and C hydrocarbons l-chloro-2-nitro-propane 2-chlorol -nitropropane dichlorotetrafluoroacetone sorbic acid and its potassium salts dodecylguanidine acetate (dodine) dodecylguanidine phthalate acetylene dicarboxylic diamide l ,2,-dicyano-1,2-dichloroethylene 1 ,2-dichloro-1-(methylsulphonyl)ethylene 1,2-dichlorol butylsulphonyl )ethylene trans-l ,2-bis-(n-propylsulphonyl )ethylene bis- 1 ,2-trichl0r0ethyl)sulphoxide bis-(n-propyl-chlorodifluorornethylthio)-sulphone diamide p-dichlorobenzene hexachlorobenzene (HCB) l,2,4-tetrachloro-4-nitrobenzene TECNACEN) pentachloronitrobenzene (QUINTAZEN) isomer mixture of 1,3,4-trichloro-2,6-dinitrobenzene and l,2,3-trichloro-4,6-dinitrobenzene 2,4,5,6-tetrachloroisophthalic nitrile 2,4-dinitrophenyl-thiocyanate diphenyl o-nitrodiphenyl l-chlor0-2,4-dinitronaph thalene 2,4,6-trichlorophenyl 2,4,5-trichlorophenyl-chloroacetate trichlorophenyl, zinc salt m-cresyl acetate 2,3,4,6-tetrachlorophenol pentachlorophenol (PCP) o-dihydroxybenzene 2,4-dioxy-n-hexylbenzene 2-phenylphenol 3,5-dibromosalicylaldehyde 2-benzyl-4-chlorophenol 2,2 '-dihydroxy-5 ,5 -dichloro-diphenylmethane CHLORPHEN) 2,2-dihydroxy-3,3',5,5,6,6'-hexachlorodiphenylmethane 2,2-dihydroxy-5,5'-dichloro-diphenylsulphide 2,2 '-dihydroxy-3,3 ',5,5 '-tetrachloro-diphenylsulphide disodium-2,2'-dihydroxy-3,3',5,5-tetrachlorodiphenylsulphide 4-chloro-o-phenylphenol l,4-dichloro-2,S-dimethoxybenzene (CHLORNEB) salicylanilide l,2-bis-( 3-methoxycarbonyl-2-thiourea)-benzene l,2-bis-( 3-ethoxycarbonyl-2-thiourea)-benzene (3,5-dimethyl-4-chlorophenoxy)-ethanol l,4-dichloro-2,5-dimethoxybenzene 2,4,5-trichl0rophenylsulphonylmethylthiocyanate phenylmercapto-methanesulphonamide 2-( l-methyl-n-propyl)-4,6-dinitrophenyl-2- methylcrotonate (BINAPACRYL) 2-(1-methyl-n-propyl)4,6-dinitrophenylisopropylcarbonate (DINOEUTON) 2-(1-methyl-n-heptyl)-4,-dinitrophenylcrotonate (DINOCAP) 4 methyl-2,6-dinitro-4-( l-ethyl-hexyl )phenylcarbonate methyl-2,6-dinitro-4-( l-propyl-pentyl)phenylcarbonate (DINOCTON) 4-nonyl-2,6-dinitro-phenylbutyrate S-methyl-2-(1-methyl-n-heptyl)-4,6-dinitrophenylthiocarbonate 1-(3,4-dichloroanilino)-l-formylamino-2,2,2-

trichloroethane 2,6-dichloro-4-nitroaniline (DICHLORAN) 2-cyanoethyl-N-phenylcarbamate propynyl-N-phenylcarbamate 2-methyl-benzoic anilide 2-iodo-benzoic anilide 2-chl oro-benzoic anilide 2,3,5,6-tetrachloro-benzoquinone 1 ANIL) 2,3-dichloro-naphthoquinone( 1,4) (DlCHLON) 2-amino-3-chloro-naphthoquinone 1,4) 2-chloro-3-acetamino-naphthoquinone(1,4) 4-methyl-2,3,5,10-tetrahydr0-3,5,lO-trioxo-4H4-H- naphtho( 2,3 ,-b )-l ,4-thiazine quinoximbenzoylhydrazone (BENQUINOX) N-(trichloromethylthio)phthalimide (FOLPET) N-(trichloromethylthio )cyclohex-4-ene-l ,2-

dicarboximide (CAPTAN) N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-l,2-

dicarboximide (CAPTAFOL) N-( l l ,2,2,-tetrachloroethylthio)cyclohex-4-enel ,2-

dicarboximide N-dichlorofluoromethylthio-NN-dim'ethyl-N phenylsulphamide (DICHLOFLUANIDE) S-(Z-pyridyl-l-oxide)-S-trichloromethyl-disulphide:-

hydrochloride sodium-N-methyl-dithiocarbamate (METHAM) sodium-N,N dimethyl-dithiocarbamate (DDC) zinc-N,N-dimethyl-dithiocarbamate (ZIRAM) iron-N,N-dimethyl-dithiocarbamate (FERBAM) disodium-ethylenel ,Z-bis-dithiocarbamate (NABAM) zinc-ethylenel ,2-bis-dithiocarbamate (ZlNEB) (1,4) (CHLOR- manganese (ID-ethylene 1,2-bis-dithiocarbamate (MANEB) zinc-propylene-l,2-bis-dithiocarbamate (MEZINEB) (PROPINEB) complex consisting of (MANEB) and zinc (MAN- COZEB) tetramethylthiuramdisulphide (THIRAM) complex consisting of (ZINEB) and polyethylene thiuramdisulphide (METIRAM) bis-(3,4-dichloro-2(5)-furanoyl)ether anhydride) Z-methoxymethyl-S-nitrofuran 5-nitro-furfuradoxime-(2) S-nitro-furfuryl-amidoxime-(2) 1-oxy-3-acetyl-6-methyl-cyclohexene-(5)dione(2,4)-

(dehydroacetic acid 4,5,6,7-tetrachlorophthalide 3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]- glutarimide (cycloheximide) phthalimide pyridine-Z-thiol-l-oxide thione a,a-bis(4-chlorophenyl)-3-pyridine-methanol (PARl- NOL) 8-hydroxyquinoline (B-QUINOLINOL) 8-hydroxyquinoline-sulphate (CHINOSOL) benzoyl8-hydroxyquinoline-salicylate (mucochloric and l-hydroxypyridine-2- To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, S granicalcium, bentonite etc. and then evaporating thesolvent. 7

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/litre to 600 g/litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

ltis also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivates (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to ethylene oxide radicals per' molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to ethylene oxide radicals per molecule and '8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e., wettable powders, pastes and emulsifiable concentrates, are agent which can be diluted with water to any concentration desired. They consist of acwith formaldehyde, condensation products of naphtha-- lene or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfated hexadecanols, heptadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with the additives mentioned above that in wettable powder, the solid particle size of from 0.02 to 0.04 and in pasts, of 0.03 is not exceeded. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents and water are used. Examples of suitable solvents are the following: alcohols, benzene, xylene, toluene, dimethyl sulfoxide, and mineral oil fractions boiling between 120 and 350C. The solvents must be practically odorless, not phytotoxic, inert to the active substances and not readily inflammable.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of the general formula I are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils alone or mixed with each other; can be used as organic solvents.

The content of active substance in the above described agents is between 0.1 percent to percent, in which connection it should be mentioned that in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5 percent or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows:

Dusts The following substances are used to manufacture a) a 5 percent and b) a 2 percent dust:

5 parts of active substance 95 parts of talcum 2 parts of active substance 1 part of highly disperse silica 97 parts of talcum.

Granules The following substances are used to produce percent granules:

5 parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0.3-0.8 mm). 10

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the IS acetone subsequently evaporated in vacuo.

Wettable powder The following constituents are used for the preparation of a) a 40 percent, b) and'c) a 25 percent, and d) a 10 percent wettable powder:

a) 40 parts of active substance,

5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silica acid. b) 25 pans of active substance,

4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture 1:1 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 pans of silica acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin. c) 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol, 1,7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, 46 parts of kaolin. d) 10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powder are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates The following substances are used to produce a) .a 10 percent and b) a 25 percent emulsifiable concentrate:

a) 10 parts of active substance, 1

3.4 pans of epoxidised vegetable oil, 13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, 40 parts of dimethylformamide, 43.2 parts of xylene. b) 25 pans of active substance,

2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture 5 parts of dimethylformamide, 57.5 parts of xylene.

From these concentrates it is possible to produce, by

EXAMPLE 1 mole) of N-chloro-cyanformimidyl chloride in 50 ml of absolute benzene is added dropwise to 300 m1 of absolute benzene which has been saturated with anhydrous ammonia. Upon completion of the dropwise addition, the reaction mixture is stirred for 1 hour at 0C, whereupon the precipitate which has formed is filtered off, The filtrate is evaporated, in the process of which a solid product is obtained. The precipitate is dissolved in 200 ml of distilled water and the solution is extracted with 2 X 150 ml of diethyl ether. The ether solutions are combined, dried and evaporated. The resulting product is combined with the product obtained from the filtrate and the whole is. recrystallised from distilled water, to give 7.9 g (38 percent of theory) of N-chlorocyanoformamidine' (m.p.l 10C Analysis of C H ClN z calculated C 23,21% H 1,95% C1 34.24% N 40,60% found C 23.07% H 1,96% C1 34.10% N 40,62%

EXAMPLE 2 Analysis of C H C1 N calculated C 15,50 H 2,60 C145,7S7r N 36.15% found C 15,4870 H 2,72% C1 45,4670 N 36,4692.

The compound used as starting products in Examples 1 and 2 can be manufactured, for example as follows: A mixture of 710 g (10.0 moles) of chlorine and g (2.5 moles) of cyanogen together with 15 g of activated charcoal is charged into an autoclave lined with tantalum and with a capacity of 1 litre. The reaction mixture is heated to 180C and kept for 7 hours at this temperature. The maximum pressure in the autoclave is bars. Non-reacted starting materials are removed by blowing out and the reaction mixture is filtered and distilled at normal pressure.

Yield of N-chloro-cyanformamidyl chloride: 123 g (40 percent of theory); b.p. lO0-l02C; mass spectrum for C Cl N :M calculated 122, M found 122.

Yield of N,N'-dichloro-oxalimido chloride: 171 g (35 percent of theory); b.p. l81l84C; mass spectrum for C2Cl4NgIM calculated 192, M found 192.

EXAMPLE 3 Nil-CH Analysis of CUH4CIN3:

calculated c 30,66% H 3,43% C130,16% N 3s,75% found c 30.57% H 3,38% Cl 30,15% N 35.73%

EXAMPLE 4 H. C-HN NH-CH.

To a solution of 15.5 g (0.5 mole) ofmethylamine in 50 ml of distilled water are added dropwise at room temperature and within minutes 18.6 (0.096 mole) of N,N "dichloro-oxalimido chloride. The reaction mixture is stirred for 1 hour at room temperature, whereupon the resulting precipitate is filtered off, washed with water and dried, to give 4.5 g (26 percent of theory) of N,N'-dichloro-N"-N"-dimethyloxalmidine which melts at 150C (with decomp.).

EXAMPLE 5 H9C4HN lilll-(l l'l To a solution of 19.4 g (0.1 mole) of N,N- dichlorooxalimido chloride in 100 ml of diethyl ether are added dropwise at 0C 29.2 g (0.4 mole) of n-butyl amine. The reaction mixture is stirred for 1 hour, whereupon the resulting precipitate is filtered off and the filtrate evaporated. The residual oil is digested with 100 ml of cyclohexane, after which the precipitate which forms is filtered off and then dried, to give 3.2 g (12 percent of theory) of N,N'- dichloro-N",N"- dibutyl-oxalamidine (mp 175C, with decomp.).

EXAMPLE 6 c1 0 c a N c1 Anhydrous ammonia is passed over the course of minutes into a previously prepared solution of 21,5 g

(0.10 mole) of N-chloro-trichloro-acetimido chloride in 250 ml of diethyl ether. The resulting ammonium chloride is filtered off and the filtrate evaporated. Recrystallisation of the reaction product from cyclohexane gives 11.0 g (56.5 percent of theory) of N- chloro-trichloro-acetamidine (m.p. 4850C).

Analysis of C l-1 Cl N,:

calculated C 12,27% H 1,03% Cl,72,40% N 14,31% found C 12,43% H 1,05% C1 73.23% N 14.22%

EXAMPLE 7 Nil-CH C C N Cl By using in Example 6 methylamine instead of anhydrous ammonia and otherwise carrying out the process as described, recrystallisation of the reaction product from cyclohexane gives 7.1 g (35 percent of theory) of N-chloro-N'-methyl-trichloro-acetamidine (m.p. 82C).

Analysis of c ,ll,,cl.N.,

calculated c 17.17% H 1,92% (167.56% N 13.35% found c 17,29% H 1.94% C167,32% N 0,32%

EXAMPLE 8 Anhydrous ammonia is passed over the course of 20 minutes into a previously prepared solution of 10.4 g (0.05 mole) of N,2,2-trichloro-cyanacetimido chloride in 100v ml of absolute benzene. The resulting ammonium chloride is filtered off and the filtrate evaporated. Recrystallisation of the reaction product from ligroin gives 7.5 g (79 percent of theory) of N,2,2-trichlorocyanacetamidine (m.p. C).

Analysis of C H Cl N z calculated C19,

3% H 1,1% Cl found C 19,4% H 1.0% Cl The N,2,2-trichloro-cyanacetimido chloride was manufactured by a process known in the art by chlorination of malodinitrile at 5560C.

EXAMPLE 9 H-CK l CH N C-C 2 Analysis of C H CIN calculated C 4l,86% H 4,22% Cl 24,73% N 29,29% found C 4l,60% H 4,l4% Cl 24,4l% N 29,15%

The following Table lists further N-chloroamidines 14 EXAMPLE 1 1 Action as seed-treatment solution The applicability of the active substances according to Examples 1 to 9 for protecting parts of plants and seeds present in the soil was demonstrated after the carrying tests had been carried out:

Action against soil fungi 500 ppm of active substance was worked into drysterilised soil by throughly mixing the two. Plastic containers of 250 ml capacity were then each filled with 100 ml of this soil. About 10 sterilised oat seeds, which were interpenetrated with mycellium of one of each of the following fungi, were placed in each of these containers beneath the surface of the soil:

Fusarium oxysporum, Pythium debaryum, Rhizoctonia solani Each of the containers was then moistened with 34 ml of distilled water and incubated at 2024C. Evaluwhich are manufactured analogous to the process de- 20 scribed in Examples l-9.

'1 A B L E Compound 01 the formula Nitrogen analysis calculated found Nil-CH I NECCC12-C=NC1 21,0 7, 21,7 7..

2'? .2 C1-N=CCC1 -C==N-Cl 23,5 Z 23,6 2

H3CHN Nth-CH I I c1--N=cCC1.,-(;=N-cl 21,0 2. 21,4 Z

NH-C.,H

. Cl C-C=N-C1 12,5 7. 12,) Z

EXAMPLE 1O Fungicidal action a) Action against Botrytis cinerea on Vicia faba Fully developed, uniformly large leaves of Vivia faba, which have been sprayed dripping wet from a spraying device with an aqueous preparation (0.1 percent content of active substance) prepared from an active substance formulated as a percent wettable powder, were placed three at a time in Petri dishes lined with filter paper. When the leaves were dry again, they were infected with. a freshly prepared, standardised spore suspension of the fungus (concentration: 100'000 spores/ml) and kept for 48 hours in a humid atmosphere at C. After this time, the leaves displayed black, initially dot-shaped specks which rapidly spread. The number and size of the infected areas served as a yardstick for determining the effectiveness of the test substance.

The compounds according to claims 1 to 9 are active against Botrytis cinerea.

ation was carried out after 5 days in order to determine whether mycellia we're growing into the surrounding soil from the seeds.

Action against seeds attacked by fungi R-HN NH-R wherein R represents hydrogen, alkyl of from 1 to 4 carbon atoms or cycloalkyl of from 3 to 6 carbon atoms; Y represents CCl and n is 0 or 1.

2. The compound of claim 1, wherein R represents 15 16 hydrogen, alkyl of from 1 to 4 carbon atoms, cyclopro- (")QFg E pyl or cyclohexy]. I

3. The compound of claim 2 of the formula 6. The compound of claim 2 of the formula H2)! NH 5 I I 2 Cl"-N=C-C=NCl ){111 4. The compound of claim 2' of the formula C N Cl t f 3 NWCH} l0 7 The compound of claim 2 of he ormula I 1 C1 -N=c -C:N c1 IFHLH Till-10H Cl-N=CCC1 -C=NCl 5. The compound of claim 2 of the formula 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1, wherein R represents hydrogen, alkyl of from 1 to 4 carbon atoms, cyclopropyl or cyclohexyl.
 3. The compound of claim 2 of the formula
 4. The compound of claim 2 of the formula
 5. The compound of claim 2 of the formula
 6. The compound of claim 2 of the formula
 7. The compound of claim 2 of the formula 